Anthraquinone and anthraquinoneazo dyestuffs



United States Patent 3,391,134 ANTIERAQUINONE AN!) ANTHRAQUINONE- AZODYESTUFFS Rudolf Kiihne and Fritz Meininger, Frankfurt am Main,

and Heinrich Froiich, Kelkheim, Taunus, Germany, assignors to FarhwerkeHoechst Aktiengesellschatt vormals Meister Lucius & Brnning, Frankfurtam Main, Germany, a corporation of Germany No Drawing. Filed June 9,1964, Ser. No. 373,862 Claims priority, application Germany, June 10,1963,

6 Claims. (03260-2071) ABSTRACT OF THE DISCLOSURE Anthraquinonedyestuffs having, as characteristic side grouping, a moiety of theformula wherein X is S O g-N Il-lower alkylcne- Y is sulfonyl orcarbonyl, R is hydrogen or lower alkyl, Z is CH CH or CH CH Cl, and m is0 or 1.

The present invention relates to new valuable reactive dyestuffs and toa process for preparing them; more particularly, it relates to reactivedyestufl's of the general Formula 1 O Nllz 3,391,134 Patented July 2,1968 "ice in which R X and m are defined as above, with about 0 to 2mols of a compound of the Formula 3 2 NSOzZ hal0gen-Y in which Y, R andZ are defined as above.

The reaction of the water-soluble starting dyestuffs with the compoundsof the Formula 3 is preferably carried out in Water. The acid halidesmay be used either in concentrated form, if desired or required withpreceding, simultaneous or subsequent addition of a substance hav ingemulsifying action or a surfactant for a better distribution in theaqueous phase, or dissolved in an organic solvent. Solvents which aresuitable for this purpose are, for example, acetone, chloroform,benzene, toluene or chlorobenzene.

The reaction temperature is determined by the reactivity of the startingsubstances. Generally, the starting dyestuffs can be reacted withsufficient speed at a temperature in the range from 0 to 50 C.,preferably from 0 to 5 C., with the condensing agents. Reactiontemperatures below 0 C. and above 50 C. can principally also be used,but then the reaction times are correspondingly longer or the yieldssmaller.

The reaction is carried out in a Weakly acid, neutral or Weakly alkalinemedium at pH-values ranging from about 3 to 9.

The hydrohalic acid that is formed when using the mentioned acid halidesis neutralized by the presence or by gradual addition of agents bindingmineral acid, for example, sodium acetate, sodium formate, sodium orpotassium carbonate or sodium or potassium bicarbonate, which are usedeither in solid form or in the form of aqueous solutions.

When the condensation reaction is complete, the watersoluble dyestuffsare precipitated, if desired after previous neutralization, from thesolutions or suspensions, filtered, Washed and dried.

The dyestuffs obtainable by the process of the present invention mayalso be prepared by reacting the starting dyestuffs with the acidhalides of the Formula 3 in an inert organic solvent. If desired ornecessary, these reactions are carried out in the presence of or whileadding acid-binding agents. Solvents which are suitable for this purposeare, for example, benzene, toluene, chlorobenzene, nitrobenzene,tetrahydrofurane, acetone, dimethyltormamide or dimethylacetamide. Theacid halides of the Formula 3, used in accordance with the presentinvention for preparing the dyestufls, constitute novel compounds.

The acid halides of the Formula 3 can be prepared for example,

(a) By reacting aminobenzenecarboxylic acids or -sulfonic acids withacylating agents which introduce the radical of the vinylsulfonic acid,for example, with carbyl sulfate or vinylsulfonic acid chloride, or

(b) By allowing, for example, acetic acid anhydride, methanesulfonicacid chloride or p-toluenesulfonic acid chloride to act onisethionylaminobenzenecarboxylic acids or -sufonic acids, whereby thehydroxyl group in [fl-position is esterified.

The benzenecarboxylic acidor benzenesulfonic acid derivatives obtainedby the methods described under (a) and (b) may be alkylated, if desired,at the nitrogen atom bound to an aromatic nucleus, with an alkylatingagent such as dimethyl sulfate or diethyl sulfate and then converted inknown manner into the corresponding carboxylic acid or sulfonic acidhalides.

The sulfonic acid chlorides of the Formula 3 may also be prepared fromaniline derivatives of the formula in which R; and Z are defined asabove, by diazotizing these compounds and subsequently reacting thediazonium salts thus obtained with sulfur dioxide in the presence ofacetic acid and copper chloride according to a process described by H.Meerwein (B. 90, 841, 1957).

As examples of such starting compounds, which are prepared in the mannerdescribed above and may be used in accordance with the process of thepresent invention, there may be mentioned the following compounds: 2 (Nmethyl ,6 chloroethylsulfonylamino)- benzene-l-carboxylic acid chloride,2 (,8 ch'loroethylsulfonylamino) benzene 1 carboxylic acid chloride. 4(N methyl B chloroethylsulfonylamino) benzene 1 carboxylic acidchloride, 3 (N methyl fichloroethylsulfonylamino) benzene 1 carboxylicacid chloride, 2 (N ethyl B chloroethylsulfonylamino) benzene 1carboxylic acid chloride, 4 (N- butyl ,8 chloroethylsulfonylamino)benzene l carboxylic acid chloride, 4 (N methylvinylsulfonylamino)benzene 1 carboxylic acid chloride or -sulfonic acid chloride, 3 (Nmethyl vinylsulfonylamino) benzene l sulfonic acid chloride, 4 (N-methyl B chloroethylsulfonylamino) 3 chlorobenzene 1 carboxylic acidchloride, 4 fi chloroethylsulfonylamino benzene 1 carboxylic acidchloride or 4 (N methyl {5' bromoethylsulfonylamino) benzene lcarboxylic acid bromide.

The dyestuffs obtained by the process of the present invention aresuitable for the dyeing or printing of various natural, regenerated orsynthetic fibrous materials such as cotton, viscose, regeneratedcellulose, wool, silk, leather, polyamides, polyacrylonitrile, celluloseacetate or aromatic polyester fibers, depending on the nature of thedyestuffs. For these purposes, the dyestuffs of the invention may beused according to the dyeing and printing methods conventionally used inthe industry, as illustrated hereinafter.

The use of the dyestulfs obtainable by the process of the presentinvention depends in the first instance on the fibrous material to bedyed and on the constitution of the dyestuff to be employed, inparticular on the numher and nature of the groups present which impartsolubility in water. For example, those of the novel dyestuffs whichpreferably contain more than one group imparting solubility in water,for example, two or more sulfonic acid and/or carboxylic acid groups inthe molecule, are especially suitable for the dyeing ofcellulose-containing materials, particularly of cotton.

The fixation of the novel dyestuffs on the cellulosecontaining fibrousmaterials dyed according to the usual dyeing or printing methods iscarried out by a treatment with an acid-binding agent, for example,sodium or potassium hydroxide, sodium or potassium carbonate, so-

dium or potassium bicarbonate, sodium silicate, sodium triphosphate orsodium trichloroacetate and, if desired, by the action of heat. Thetreatment with the acid-binding agent can be carried out prior to,during or after the application of the dyestuff.

Thus, for example, cellulose-containing textile materials can be dyedaccording to the so-called direct dyeing method, by treating the textilematerials with an aqueous solution of the dyestutf in the presence ofacid-binding agents at a temperature in the range of, for example, 40and C.

For preparing dyeings, one may also apply the dyestuif to thecellulose-containing textile material according to the usual dyeing andpadding methods and then introduce the goods dyed into an aqueoussolution of the acid-binding agent at a temperature in the range of 20and 100 C.

Furthermore, the novel dyestuffs may be applied, for example, by paddingor from a dyebath at a temperature ranging from 20 to 100 C. to thetextile material impregnated with an aqueous solution of theacid-binding agent, and heating, if desired, after intermediate drying.

Furthermore, the textile material may be treated with an aqueoussolution of the dyestutf in the presence of the acid-binding agent,squeezed and then allowed to remain at room temperature or heated for ashort period, for example, by steaming, if desired, after anintermediate drying.

The aqueous dyestuif solutions used for preparing the dyeings may becombined with other substances; thus, there may be added above allelectrolytes such as sodium chloride or sodium sulfate, urea, dispersingagents, surfactants and thickeners, for example, sodium alginate.

The novel dyestuffs are also suitable for the preparation of prints oncellulose materials. For this purpose, the fabric is printed with aprinting paste containing the acid-binding agent and subjected to ashort heat treatment, if desired, after intermediate drying. It is alsopossible to apply a printing paste containing one or several of thedyestuffs obtainable by the process of the invention to the cellulosefabric impregnated with an acidbinding agent, and subsequently to heatthe printed fabric, for example, by steaming. Furthermore, the cellulosematerials may first be printed with a printing paste containing one orseveral dyestuffs, and then treated with the aqueous solution ofacidbinding agents, preferably in the presence of electrolytes such assodium chloride or sodium sulfate at a temperature in the range fromabout 60 to 100 C. The printing pastes used for preparing the prints mayalso contain further substances, for example, urea, thickeners,water-in-oil emulsions, surfactants and m-nitrobenzenesulfonic sodium.The dyeing and prints on cellulose prepared with the novel dyestuffs aregenerally rinsed after the dyeing or printing process with water, thensoaped and rinsed again with water before drying.

Finally, the novel dyestuffs may also be used for the dyeing ofnitrogen-containing textile materials, for example, wool and polyamidefibers. The dyeing is carried out from weakly alkaline, neutral or aciddyebaths in the presence of compounds conventionally used for the dyeingof nitrogen-containing textile materials, for example, sodium sulfate,ammonium acetate, surfactants such as quaternary ammonium salts, andnon-ionic dispersing agents. If desired, the pH-value of the dyebath maybe varied during the dyeing process by adding alkalies or alkaline saltsor by adding acids or acid salts, for example, in such a manner as tostart the dyeing at a pH- value of 4 and increasing the pH-value duringthe dyeing to 7.5.

The novel dyestuffs give in general full and clear shades which aredistinguished by good properties of fastness, especially by good to verygood fastness to light and wet processing.

The following examplesillustrate the invention, but they are notintended to limit it hereto.

Example 1 71 parts by Weight of the trisodium salt of the dyestuff ofthe following formula prepared by condensation of 1-amino-4bromoanthraquinone-Z-sulfonic acid with4,4'-diaminodiphenyl-2,2'-disulfonic acid, are dissolved in 1650 partsby volume of water. Into this solution, there are introduced dropwise,while stirring intensely, at to 5 C., a solution of 32.6 parts by weightof 4-(N-methyl-(B-chloroethylsulfonylamino)=benzene-1-car-boxylic acidchloride in 100 parts by volume of chloroform and, simultaneously, anaqueous sodium carbonate solution having a strength of by weight, in amanner such that the pH-value is kept at 6 to 7. After 12 hours, thecondensation is complete. The chloroform is then distilled ott. Thedyestuff formed is salted out with potassium chloride, filtered off anddried. The dyestutf constitutes a blue powder which dissolves in Waterto give a blue solution.

The dyestuff has the formula m p aquinoneamino)-bcnzene-l-isoeya-,3,2,-trrsulton1e acid. Hate Example 2 60 parts by Weight of thetri-sodium salt of the dyestutl of the formula N 80311 SO3H prepared bycondensation of 1-amino-4-bromoanthraquiuone-Z-sulfonic acid with4,4'-diamino stilbene-2,2'-

and gives a blue dyeing on cotton which is fast to light, to washing andto boiling.

Similar dyestuffs are obtained when using the parts by weight indicatedin the above example of the anthraquinone dyestuffs listed in thefollowing table and reacting them with the respective acylatingcomponents listed in the second column.

disulfonic acid, are dissolved at 30 C. in 2150 parts by volume ofwater. Into the dyestutf solution obtained, there are introduced bystrewing in, while stirring vigorously in the course of 2 hours, partsby Weight of4-(N-methylfi-chloroethylsulfonylamino)-'benzene-1-carboxylic acid inthe form of a finely ground powder. Simultaneously, a saturated sodiumbicarbonate solution is added dropwise so that the pH-value is kept at 5to 5.5. As soon as the condensation is complete, the precipitatedproduct is filtered ofi and washed with a sodium chloride solutionhaving a strength of 5% by weight. The filter residue is dissolved in2500 parts by volume of Water at 95 C.; 3 parts by weight of kieselguhrand 2 parts by Weight of animal charcoal are added to this solution. Themixture is stirred for one quarter hour at 95 C. and filtered. After thefiltrate has cooled, the product is precipitated by means of sodiumchloride, filtered off and dried under reduced pres sure at 50 to C. Thedyestulf obtained which in the form of the free acid has the formulaSOIXH r Ha Q stulf of the formula (l NH-Q-sOnI are introduced, withstirring, into 150 parts by weight of N-methyl-pyrrolidone. 18.5 partsby weight of 3-(N- methyl vinylsulfonylamino) benzene 1 carboxylic acidchloride are added portionwise at 30 C. to the mixture which issubsequently stirred for 1% hours at 30 to 40 C. As soon as the reactionis complete, the mixture is allowed to run into 300 parts by volume ofsaturated sodium chloride solution. The separated product is isolated byfiltration and dissolved in 500 parts by volume of water. The dyestufisolution thus obtained is filtered and combined with by weight of sodiumchloride (referred to the volume). The precipitate is then filtered off,washed with a dilute sodium chloride solution and dried under reducedpressure at 40 to 50 C.

The dyestufi? obtained, which in the form of the free acid has theformula l SO H in the form of the sodium salt are dissolved in 1775parts by volume of water. To this solution, there are added dropwise, at30 to 35 C., 45 parts by weight of 4-(N-methyl B chloroethylsulfonylamino)-be11- zene-l-carboxylic acid chloride and,simultaneously, an aqueous sodium carbonate solution in such a mannerthat the reaction mixture always shows a neutral reaction.

As soon as the condensation is complete, the dyestufi formed iscompletely salted out by introduction of sodium chloride, filtered ofi,washed with a dilute sodium chloride solution and dried under reducedpressure. The pure dyestutf which in the form of the free acid has theabove formula (the sulfonic acid group in the nucleus A is in 5- or 8-position) dissolves in water to give an olive green solution and dyescotton, in the presence of sodium triphosphate, olive green tints whichare fast to light and to washing.

Example 5 53.3 parts by weight of the di-sodium salt of the dyestufi" ofthe formula l I lH s oan prepared by sulfonation of1-amino-4-(4'-aminophenylamino) anthraquinone 2 sulfonic acid, aredissolved at 40 C. in 890 parts by volume of water. To this solution,there are added dropwise, at 35 to 40 C., in the course of 1 hour, whilestirring vigourously, 50.2 parts by weight of 4 (N-methyl ,8chloroethylsulfonylamino)-benzene 1 sulfonic acid chloride dissolved in110 parts by volume of acetone and, simultaneously, an aqueous sodiumcarbonate solution in such a manner that the solution always has apH-Value of 6.5 to 7.0. As soon as the reaction is complete,precipitation of the formed dyestufi having the formula SOgI-I gives, inthe presence of sodium bicarbonate, blue prints is completed by theaddition of sodium chloride, the dyeon cotton that have a good fastnessto washing and to light.

Example 4 57.4 parts by weight of the dyestutf of the formula 0 NH: II Is03n 1IO3Sv-A I soar (the sulfonic acid group in the benzene nucleus Ais in 5 or 8-position) 9 are stirred in the manner described in Example1, at a pH-value of 7.5 to 9, with 30 parts by weight of4-(fi-chloroethylsulfonylamino)-benzene-l-carboxylic acid chloride. Ablue dyestuif powder is obtained which dissolves in water to give a bluesolution.

The dyestuif which has the formula II I H038 O gives, in the presence ofsodium carbonate, a blue print 30 constitutes a dark blue powder whichdissolves in water on cotton which is very fast to washing and to light.

Example 7 53.3 parts by weight of the di-sodium salt of the dyestuff ofthe formula 0 NH; II

r) lira-4111:

to give a blue solution and which dyes cotton fast blue tints, whenapplied in the presence of sodium carbonate or sodium hydroxide.

When using the above example 46.5 parts by weight of 4(N-ethyl-;3-chloroethylsulfonylamino)-benzene-1- carboxylic acidchloride or 50.7 parts by weight of 4-(N-butyl-B-chloroethylsulfonylamino) benzene-l-carboxylic acid chlorideinstead of 45 parts by weight of 4-(N-metl1-yl-B-chloroethylsulfonylarnino)-benzene-1-carboxylic acid chloride,dyestuffs having similar properties are obtained.

Dyestuffs that have similar properties are also obtained when reactingthe anthraquinone dyestuffs (I) listed in the following table undercorresponding reaction condi- 45 tions with the respective acidchlorides (II).

I II

Anthraquiuone dyestufi Acylating component Tint on cotton 1 O NH:4-(N-methyl-vlnylsulfouylamino)-benzene-l Blue.

sulfonic acid chloride. sour K/ S 03H I l O NH NH:

2 O NH: 3-(N-methyl-B-chloroethylsulfonylamino)- Do.

I] I benzene-l-carboxylic acid chloride. (:l I sour I! I O NH l S Oz-NH--SOsH I II Anthraquinone dyestufi Acylating component Tint on cotton 3O NH 3-(N-methyl- S-chloroethylsulfonylamino)- Blue. II Ibcnzone-l-carboxylic acid chloride. 1 l (S0311 JO-NH-QAS 0 311 I NI I] 40 NH; 4-(N-methyl-B-ch1oroethylsulionylamino)- Do.

II benzene-l-carboxylic acid chloride. I 303K I I 0 NH O HzNH2 5 ii)....(10 D0.

SC I-I HO sS- I l I s 0 :NH-CHgCII5-NH1 (The Sulfonic acid group is in5- or 8-position) 6 H03? (I? NH: (10 Do.

(:Llj II I O NH- NH1 7 fl) IITH: --..-d0 Do.

I S 03H HOsSk/b II I 0 NH NH1 I SOQH 8 (H) NH; v....d0 Green.

SO31! H03S l 80 K I I I (The SO ll-group is in 5- or 8-positi0n) 9 O NH; 4-(N-methyl-vinylsulfonylamino)-benzene-1- Blue.

II carboxylic acid chloride. l l S0311 II I O N H -NHz S OzNI-I-l0weralkyleue Q CII=CII sour sour W I I Y represents a member selected fromthe group consistf 1 ing of sulfonyl and carbonyl, R represent a memberse- SOBH SOsH $0311 10 lected from the group consisting of hydrogen andlower X alkyl, Z represents a member selected from the group consistingof --cH=cH and -CH -CH -Cl, and m represents a number from 0 to 1.

3. The dyestulf of the formula 4. The dyestufi' of the formula (I?IIIIIQ HOaSO -s0ur Y (r3113 I 0 NII -N=N NHC o -NSO:CH2CH2CI 5. Thedyestuff of the formula NIT; l l SO3H HOaS 6. The dyestufi of theformula 0 NH: II I l IHO o-Q-rL-s ol01-no Hz-Cl UNITED STATES PATENTS3,154,567 10/1964 Eisele et a1 260-372 CHARLES P. PARKER, PrimaryExaminer.

D. M. PAPUGA, Assistant Examiner.

